WO2019013165A1 - Batterie rechargeable au magnésium, solution électrolytique et procédé de fabrication d'une solution électrolytique - Google Patents

Batterie rechargeable au magnésium, solution électrolytique et procédé de fabrication d'une solution électrolytique Download PDF

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WO2019013165A1
WO2019013165A1 PCT/JP2018/025887 JP2018025887W WO2019013165A1 WO 2019013165 A1 WO2019013165 A1 WO 2019013165A1 JP 2018025887 W JP2018025887 W JP 2018025887W WO 2019013165 A1 WO2019013165 A1 WO 2019013165A1
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magnesium
sulfone
solvent
electrolyte
electrolytic solution
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PCT/JP2018/025887
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English (en)
Japanese (ja)
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隆平 松本
秀樹 川▲崎▼
森　大輔
有理 中山
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株式会社村田製作所
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Priority to JP2019529712A priority Critical patent/JP7014228B2/ja
Publication of WO2019013165A1 publication Critical patent/WO2019013165A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to an electrolytic solution, a magnesium secondary battery provided with such an electrolytic solution, and a method of manufacturing the electrolytic solution.
  • the electrolytic solution is composed of, for example, a magnesium salt and a solvent in which the magnesium salt is dissolved.
  • a positive electrode active material for example, sulfur
  • a solvent in which the magnesium salt is dissolved.
  • An electrolyte comprising a magnesium salt and a sulfone in which a magnesium salt is dissolved is known, for example, from JP-A-2014-072031 (Patent Document 1), and the electrolyte disclosed in this patent publication has excellent performance.
  • the value of (the number of moles of sulfone) / (the number of moles of magnesium constituting the magnesium salt) (hereinafter, for convenience, may be referred to as "Mg molar ratio" )
  • Mg molar ratio" Has a high value of 8, for example. Therefore, by reducing the proportion of the solvent in a state in which the interaction with the electrolyte constituting the electrolyte solution is weak, it is possible to provide an electrolyte solution having more excellent properties and a magnesium secondary battery provided with the same.
  • an object of the present disclosure is to provide an electrolytic solution having more excellent characteristics, a magnesium secondary battery provided with such an electrolytic solution, and a method of producing an electrolytic solution which can easily manufacture such an electrolytic solution. It is to do.
  • An electrolytic solution according to a first aspect of the present disclosure for achieving the above object comprises: A solvent comprising sulfone, and a magnesium salt dissolved in the solvent; The value of (the number of moles of sulfone) / (the number of moles of magnesium constituting the magnesium salt) (Mg molar ratio) is 4 or less, preferably less than 4, and thus the interaction with the electrolyte is weak The solvent is being reduced.
  • An electrolytic solution according to a second aspect of the present disclosure for achieving the above object comprises: An electrolyte comprising a solvent comprising sulfone and a magnesium salt dissolved in the solvent, In Raman spectroscopy measurement, when (number of moles of sulfone) / (number of moles of magnesium constituting magnesium salt) is different among the measurement peaks, based on the peak value of Raman spectrum intensity with the least change in peak position or intensity , The Raman spectrum intensity of the electrolyte and the Raman spectrum intensity of the solvent are normalized, and the Raman spectrum intensity of the solvent alone at the value RS 1 of the Raman shift of the solvent having no interaction with the electrolyte is I 11 .
  • the Raman spectral intensity of the electrolytic solution is I 22, I 12 / I 11 ⁇ 0.6 Or 0.4 ⁇ I 22 / I 21 Satisfy.
  • An electrolytic solution according to a third aspect of the present disclosure for achieving the above object is: A solvent comprising sulfone, and a magnesium salt dissolved in the solvent; The ratio of solvent molecules strongly interacting with the dissolved magnesium salt to magnesium is 0.5 or more.
  • An electrolytic solution according to a fourth aspect of the present disclosure for achieving the above object comprises: A solvent comprising sulfone, and a magnesium salt dissolved in the solvent; The value of (mole number of sulfone) / (mole number of magnesium constituting magnesium salt) (Mg mole ratio) is less than 4.
  • the magnesium secondary battery according to the first to fourth aspects of the present disclosure for achieving the above object comprises a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and an electrolytic solution It is a magnesium secondary battery equipped with
  • the electrolytic solution comprises the electrolytic solution according to the first aspect of the present disclosure.
  • the electrolytic solution comprises the electrolytic solution according to the second aspect of the present disclosure.
  • the electrolyte comprises the electrolyte according to the third aspect of the present disclosure.
  • the electrolytic solution comprises the electrolytic solution according to the fourth aspect of the present disclosure.
  • a method of producing an electrolytic solution of the present disclosure to achieve the above object is a solvent comprising sulfone, and a method of producing an electrolytic solution comprising a magnesium salt dissolved in the solvent, After grinding the magnesium salt, mix with solvent, heat and stir.
  • the electrolytic solution according to the first aspect of the present disclosure or the electrolytic solution in the magnesium secondary battery according to the first aspect of the present disclosure are collectively referred to as “the first aspect of the present disclosure
  • the value (Mg molar ratio) of (number of moles of sulfone) / (number of moles of magnesium constituting magnesium salt) is defined.
  • the solvent in the state of weak interaction with the electrolyte is reduced.
  • the electrolytic solution according to the second aspect of the present disclosure or the electrolytic solution in the magnesium secondary battery according to the second aspect of the present disclosure are collectively referred to In the electrolyte solution etc. which concern on aspect of 2, the ratio of the Raman spectrum intensity
  • the electrolytic solution according to the third aspect of the present disclosure or the electrolytic solution in a magnesium secondary battery according to the third aspect of the present disclosure (hereinafter, these electrolytic solutions are collectively referred to In the electrolytic solution and the like according to the third aspect), the abundance ratio of solvent molecules strongly interacting with the dissolved magnesium salt to magnesium is specified.
  • the electrolytic solution according to the fourth aspect of the present disclosure or the electrolytic solution in a magnesium secondary battery according to the fourth aspect of the present disclosure are collectively referred to
  • the value of (mole number of sulfone) / (mole number of magnesium constituting magnesium salt) (Mg molar ratio) is defined. . Therefore, the proportion of the solvent in the state of weak interaction with the electrolyte can be reduced, and it becomes possible to provide an electrolytic solution having more excellent properties and a magnesium secondary battery provided with the same.
  • the effects described in the present specification are merely examples and are not limited, and may have additional effects.
  • FIG. 1 is a schematic exploded view of a magnesium secondary battery of Example 1.
  • FIG. 2A is a graph showing the results of Raman spectroscopy measurement of the electrolytes of Example 1A, Example 1B, Example 1C and Comparative Example 1, and FIG. 2B shows strong interaction with the dissolved magnesium salt. It is a graph showing the result of finding the relationship between C s / C Mg and I f / C Mg in order to estimate the abundance ratio of solvent molecules to magnesium.
  • FIG. 3 is a graph showing the results of tripolar cyclic voltammetry (CV) measurement in the electrolyte solution of Example 1B.
  • FIG. 4 is a schematic cross-sectional view of the electrochemical device (capacitor) of Example 2.
  • FIG. 1 is a schematic exploded view of a magnesium secondary battery of Example 1.
  • FIG. 2A is a graph showing the results of Raman spectroscopy measurement of the electrolytes of Example 1A, Example 1B, Example 1C and Comparative Example 1, and FIG. 2
  • FIG. 5 is a conceptual view of an electrochemical device (air battery) of Example 2.
  • FIG. 6 is a conceptual view of an electrochemical device (fuel cell) of Example 2.
  • FIG. 7 is a schematic cross-sectional view of a magnesium secondary battery (cylindrical magnesium secondary battery) in Example 3.
  • FIG. 8 is a schematic cross-sectional view of a magnesium secondary battery (flat plate type laminated film type magnesium secondary battery) in Example 3.
  • FIG. 9 is a block diagram showing a circuit configuration example in the third embodiment in which the magnesium secondary battery of the present disclosure described in the first embodiment is applied to a battery pack.
  • FIGS. 10A, 10B, and 10C are block diagrams showing the configuration of an application example (electric vehicle) of the present disclosure in the third embodiment, and represent the configuration of an application example (power storage system) of the present disclosure in the third embodiment.
  • FIG. 18 is a block diagram and a block diagram illustrating a configuration of an application (power tool) of the present disclosure in the third embodiment.
  • FIG. 11 is a conceptual view of a magnesium secondary battery of the present disclosure.
  • Example 1 A magnesium secondary battery and an electrolyte according to the first to fourth aspects of the present disclosure, and a method of producing the electrolyte
  • Example 2 Modification of Example 1
  • Example 3 Application Example of Magnesium Secondary Battery of Example 1 5.
  • the electrolytic solution according to the first to fourth aspects of the present disclosure or alternatively, the electrolytic solution in a magnesium secondary battery according to the first to fourth aspects of the present disclosure
  • the sulfone is represented by R 1 R 2 SO 2 (wherein R 1 and R 2 each independently represent an alkyl group) Alkyl sulfone or an alkyl sulfone derivative.
  • R 1 and R 2 are each independently, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and / or t -Butyl and the like.
  • alkyl sulfone specifically, dimethyl sulfone (DMS), methyl ethyl sulfone (MES), methyl n-propyl sulfone (MnPS), methyl i-propyl sulfone (MiPS), methyl n-butyl sulfone (MnBS) ), Methyl-i-butyl sulfone (MiBS), methyl-s-butyl sulfone (MsBS), methyl-t-butyl sulfone (MtBS), ethyl methyl sulfone (EMS), diethyl sulfone (DES), ethyl-n-propyl Sulfone (EnPS), Ethyl-i-propyl sulfone (EiPS), Ethyl-n-butyl sulfone (EnBS), Ethyl-i-butyl sulfone (EiBS), E
  • alkyl sulfone derivative ethyl phenyl sulfone (EPhS) can be mentioned. And, among these sulfones, at least one selected from the group consisting of EnPS, EiPS, EsBS and DnPS is preferable.
  • the magnesium salt can be in the form of MgX n (where n is 1 or 2 and X is a monovalent or divalent anion) .
  • X can be in the form of a molecule containing halogen, -SO 4 , -NO 3 or a hexaalkyl disiazide group.
  • magnesium fluoride [MgF 2 ], magnesium chloride [MgCl 2 ], magnesium bromide [MgBr 2 ], and / or magnesium iodide [MgI 2 ] can be mentioned.
  • the magnesium salt is a mixture of MgCl 2 and Mg (TFSI) 2 [magnesium bistrifluoromethanesulfonyl imide], magnesium perchlorate [Mg (ClO 4 ) 2 ], magnesium nitrate [Mg (NO 3 ) 2 ]
  • Magnesium sulfate [MgSO 4 ] magnesium acetate [Mg (CH 3 COO) 2 ], magnesium trifluoroacetate [Mg (CF 3 COO) 2 ], magnesium magnesium borohydride [Mg (BH 4 ) 2 ], tetrafluoroboronic acid
  • magnesium salt-A The magnesium salt mentioned above from magnesium fluoride to [Mg (HRDS) 2 ] is referred to as “magnesium salt-A” for convenience.
  • Such an electrolytic solution or the like of the present disclosure is a magnesium ion-containing non-aqueous electrolytic solution in which a magnesium salt -A is dissolved in a solvent comprising sulfone.
  • the sulfone contains ethyl-n-propylsulfone (EnPS), and the magnesium salt contains magnesium chloride (MgCl 2 ), preferable.
  • the Mg molar ratio is defined. This value in the electrolyte can be determined based on the ratio of the number of input moles of sulfone and magnesium salt in preparation of the electrolyte.
  • the Mg molar ratio in the electrolytic solution can be determined from Raman spectroscopy, elemental analysis or the like.
  • the peak value of the Raman spectral intensity with the least change in peak position or intensity may be determined by comparing the measured data with baseline corrected data in the range of 600 cm ⁇ 1 to 1180 cm ⁇ 1 .
  • the Raman spectrum intensity of the electrolyte and the Raman spectrum intensity of the solvent are normalized based on this peak value, specifically, the Raman spectrum intensity of the electrolyte and the Raman spectrum intensity of the solvent at this peak value are It is sufficient to correct (normalize) the entire Raman spectrum intensity of the electrolyte and the entire Raman spectrum intensity of the solvent so as to be equal.
  • the Raman shift value RS 1 of the solvent having no interaction with the electrolyte can be obtained by repeating the peak separation and the peak fitting of the spectrum after baseline correction. Peak fitting can be performed using the Gaussian function and the Lorentzian complex function without limiting the Raman shift value.
  • the value RS 2 of the Raman shift of the solvent strongly interacting with the electrolyte (or interacting with the electrolyte) can be obtained by the same method as the method of obtaining the value RS 1 of Raman shift. Also, the strength of interaction can be quantified based on Raman shift (shift of peak position).
  • the plurality of Raman shift the total Raman spectral intensity in the value RS 1 may be set to I 11.
  • the abundance ratio of solvent molecules strongly interacting with the dissolved magnesium salt in the electrolytic solution etc. according to the third aspect of the present disclosure to magnesium may be determined based on the method described in detail in Example 1.
  • the magnesium salt can include magnesium borohydride (Mg (BH 4 ) 2 ).
  • Mg (BH 4 ) 2 magnesium borohydride
  • Such an electrolytic solution can be produced by dissolving magnesium borohydride in sulfone.
  • a magnesium salt consisting of magnesium borohydride (Mg (BH 4 ) 2 ) is conveniently referred to as “magnesium salt-B”.
  • Such an electrolytic solution or the like of the present disclosure is a magnesium ion-containing non-aqueous electrolytic solution in which a magnesium salt -B is dissolved in a solvent comprising sulfone.
  • R 1 R 2 SO 2 An alkyl sulfone or an alkyl sulfone derivative represented by R 1 R 2 SO 2 (wherein R 1 and R 2 each independently represent an alkyl group) in an electrolytic solution or the like of the present disclosure containing a magnesium salt-B It can be done.
  • the type (carbon number and combination) of R 1 and R 2 is not particularly limited, and is selected as necessary.
  • the carbon number of each of R 1 and R 2 is preferably 4 or less, but is not limited thereto.
  • the sum of the carbon number of R 1 and the carbon number of R 2 is preferably 4 or more and 7 or less, but is not limited thereto.
  • R 1 and R 2 are each independently, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and / or t -Butyl group can be mentioned.
  • alkyl sulfone in the electrolytic solution of the present disclosure containing magnesium salt-B examples include dimethyl sulfone (DMS), methyl ethyl sulfone (MES), methyl-n-propyl sulfone (MnPS), and methyl-i- Propyl sulfone (MiPS), methyl-n-butyl sulfone (MnBS), methyl-i-butyl sulfone (MiBS), methyl-s-butyl sulfone (MsBS), methyl-t-butyl sulfone (MtBS), ethyl methyl sulfone EMS), diethyl sulfone (DES), ethyl-n-propyl sulfone (EnPS), ethyl-i-propyl sulfone (EiPS), ethyl-n-butyl sulfone (EnBS), ethyl-
  • alkyl sulfone derivative ethyl phenyl sulfone (EPhS) can be mentioned. And, among these sulfones, at least one selected from the group consisting of EnPS, EiPS, EsBS and DnPS is preferable.
  • An additive may be further contained in the electrolytic solution and the like of the present disclosure as required.
  • metal ions such as aluminum (Al), beryllium (Be), boron (B), gallium (Ga), indium (In), silicon (Si), tin (Sn), titanium (Ti)
  • salts consisting of cations of at least one atom or group selected from the group consisting of chromium (Cr), iron (Fe), cobalt (Co) and lanthanum (La).
  • the electrolytic solution and the like of the present disclosure using the magnesium salt-A can be produced, for example, by the method of producing the electrolytic solution of the present disclosure described above. After dissolving magnesium salt-A in a low boiling point solvent in which magnesium salt-A is soluble, The sulfone is dissolved in a solution of magnesium salt-A in a low boiling point solvent, and then Remove the low boiling point solvent from the solution in which the sulfone is dissolved, It can manufacture based on each process.
  • any solvent having a boiling point lower than that of the selected sulfone among the solvents in which the magnesium salt-A is soluble can basically be used.
  • alcohol is preferably used.
  • the alcohol may be a monohydric alcohol or a polyhydric alcohol, and may be a saturated alcohol or an unsaturated alcohol.
  • the alcohol examples include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol (sec-butanol), 2-methyl-1-propanol (isobutanol), 2- Mention may be made, without limitation, of methyl 2-propanol (tert-butanol) and / or 1-pentanol and the like. It is preferable to use dehydrated alcohol as the alcohol.
  • magnesium salt -A is dissolved in alcohol.
  • anhydrous magnesium salt can be used as magnesium salt -A.
  • magnesium salt-A is not soluble in sulfone but is well soluble in alcohol.
  • alcohol coordinates to magnesium.
  • the sulfone is dissolved in an alcohol in which the magnesium salt-A is dissolved.
  • the alcohol is then removed by heating the solution under reduced pressure.
  • the alcohol coordinated to magnesium is exchanged (or substituted) with the sulfone.
  • a magnesium ion-containing non-aqueous electrolytic solution which can be used for magnesium metal by using sulfone which is a non-ether solvent and exhibits electrochemical dissolution reaction of magnesium at room temperature. it can.
  • This electrolytic solution has a low volatility because it has a higher boiling point than ether solvents such as THF (tetrahydrofuran) generally used, and because it uses sulfone with high safety as a solvent, handling becomes easy . Therefore, for example, the process in the case of manufacturing a magnesium ion battery can be greatly simplified.
  • this electrolytic solution has a wider potential window than a conventional electrolytic solution using THF as a solvent, the choice of the positive electrode material of the magnesium ion secondary battery is expanded, and the voltage of the secondary battery which can be realized, ie, The energy density can be improved. Furthermore, since this electrolytic solution has a simple composition, the cost of the electrolytic solution itself can be significantly reduced.
  • the electrolytic solution or the like of the present disclosure has a solvent comprising a sulfone and a nonpolar solvent, and a magnesium salt-A dissolved in the solvent.
  • the nonpolar solvent is selected as necessary, but is preferably a non-aqueous solvent having a relative dielectric constant and a number of donors of 20 or less.
  • the nonpolar solvent more specifically, for example, at least one nonpolar solvent selected from the group consisting of aromatic hydrocarbons, ethers, ketones, esters and chain carbonates can be mentioned.
  • the aromatic hydrocarbon include toluene, benzene, o-xylene, m-xylene, p-xylene, and / or 1-methylnaphthalene.
  • the ether for example, diethyl ether and / or tetrahydrofuran can be mentioned.
  • the ketone for example, 4-methyl-2-pentanone and the like can be mentioned.
  • ester methyl acetate and / or ethyl acetate etc. can be mentioned, for example.
  • chain carbonate for example, dimethyl carbonate, diethyl carbonate and / or ethyl methyl carbonate can be mentioned.
  • the sulfone and magnesium salt-A are as described above. Moreover, you may add the additive mentioned above to electrolyte solution as needed.
  • solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, ⁇ -butyrolactone and / or tetrahydrofuran may also be used as a solvent.
  • solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, ⁇ -butyrolactone and / or tetrahydrofuran may also be used as a solvent.
  • one of them may be used alone, or two or more of them may be mixed and used.
  • the electrolyte and the like of the present disclosure using a magnesium salt-A and a nonpolar solvent are, for example, After dissolving magnesium salt-A in a low boiling point solvent in which magnesium salt-A is soluble, The sulfone is dissolved in a solution of magnesium salt-A in a low boiling point solvent, and then After removing the low boiling point solvent from the solution in which the sulfone is dissolved, Mixing the nonpolar solvent with the solution from which the low boiling point solvent has been removed, It can manufacture based on each process.
  • magnesium salt -A is dissolved in alcohol. This coordinates alcohol to magnesium.
  • anhydrous magnesium salt can be used as magnesium salt -A.
  • the sulfone is dissolved in an alcohol in which the magnesium salt is dissolved.
  • the alcohol is then removed by heating the solution under reduced pressure.
  • the alcohol coordinated to magnesium is exchanged (or substituted) with the sulfone.
  • the nonpolar solvent is mixed with the solution from which the alcohol has been removed.
  • the electrolyte layer can also be composed of the electrolytic solution of the present disclosure and the like, and a polymer compound composed of a holder that holds the electrolytic solution.
  • the polymer compound may be swollen by an electrolytic solution.
  • the polymer compound swollen by the electrolytic solution may be in the form of gel.
  • polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene or polyethylene oxide is preferable from the viewpoint of electrochemical stability.
  • the electrolyte layer can also be a solid electrolyte layer.
  • the positive electrode member contains sulfur or a sulfur compound.
  • the positive electrode member contains a sulfur or a sulfur compound A positive electrode active material comprising an active material layer or, alternatively, a positive electrode member comprising a positive electrode current collector and a sulfur or sulfur compound formed on the positive electrode current collector (on one side or both sides of the positive electrode current collector) Has a layer.
  • sulfur include S 8 sulfur and polysulfides, and examples of sulfur compounds include insoluble sulfur, colloidal sulfur and / or organic sulfur compounds (such as disulfide compounds and trisulfide compounds).
  • the positive electrode current collector is, for example, metal foil or alloy foil such as nickel, stainless steel and / or molybdenum, metal plate, alloy plate, metal mesh, alloy mesh, carbon fiber or carbon It consists of carbon materials, such as a sheet.
  • the positive electrode member may have a structure including only the positive electrode active material layer (layered positive electrode active material) without the positive electrode current collector.
  • the positive electrode active material layer may optionally contain at least one of a conductive additive and a binder.
  • the negative electrode member contains magnesium or a magnesium compound.
  • the negative electrode member is made of magnesium (magnesium metal alone), a magnesium alloy or a magnesium compound.
  • the negative electrode active material layer may be formed on the surface of the negative electrode current collector constituting the negative electrode member.
  • the negative electrode active material layer is composed of a layer having magnesium ion conductivity.
  • a magnesium (Mg) based material can be mentioned, and further, It may contain at least carbon (C), oxygen (O), sulfur (S) and halogen. It is preferable that such a negative electrode active material layer have a single peak derived from magnesium in the range of 40 eV or more and 60 eV or less.
  • halogen for example, at least one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) can be mentioned.
  • F fluorine
  • Cl chlorine
  • Br bromine
  • I iodine
  • the oxidation state of magnesium is substantially constant from the surface of the negative electrode active material layer in the depth direction to 2 ⁇ 10 ⁇ 7 m.
  • the back surface of the negative electrode active material layer means the surface on the side constituting the interface between the negative electrode current collector and the negative electrode active material layer, of the both surfaces of the negative electrode active material layer, and the surface of the negative electrode active material layer And means the surface opposite to the back surface of the negative electrode active material layer.
  • the negative electrode active material layer contains the above-described elements can be confirmed based on XPS (X-ray Photoelectron Spectroscopy). Moreover, it can confirm similarly that the negative electrode active material layer has the said peak, and the oxidation state of magnesium based on a XPS method.
  • the negative electrode active material layer may optionally contain at least one of a conductive additive and a binder.
  • the negative electrode member is made of, for example, a plate-like material or a foil-like material, but is not limited thereto, and may be formed (shaped) using powder. As described above, the negative electrode member may include the negative electrode current collector. As a material which comprises a negative electrode collector, metal foil or alloy foils, such as copper, nickel, stainless steel, molybdenum, magnesium and / or a magnesium compound, a metal plate, and an alloy plate can be mentioned.
  • carbon materials such as graphite, carbon fiber, carbon black, a carbon nanotube
  • VGCF vapor growth carbon fiber
  • carbon black for example, acetylene black and / or ketjen black
  • MWCNT multi-wall carbon nanotube
  • SWCNT single wall carbon nanotube
  • DWCNT double wall carbon nanotube
  • materials other than carbon materials can be used, and for example, metal materials such as Ni powder, conductive polymer materials, and the like can be used.
  • a binder contained in the positive electrode active material layer or the negative electrode active material layer for example, a fluorine resin such as polyvinylidene fluoride (PVdF) and / or polytetrafluoroethylene (PTFE), a polyvinyl alcohol (PVA) resin and / or Alternatively, polymer resins such as styrene-butadiene copolymer rubber (SBR) resins can be used.
  • a conductive polymer may be used as a binder.
  • the conductive polymer for example, substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and / or (co) polymer consisting of one or two or more selected from these can be used.
  • the positive electrode member and the negative electrode member are separated by an inorganic separator or an organic separator which allows magnesium ions to pass while preventing a short circuit due to the contact of both electrodes.
  • an inorganic separator a glass filter and / or glass fiber can be mentioned, for example.
  • the organic separator include porous membranes made of synthetic resin made of polytetrafluoroethylene, polypropylene and / or polyethylene, etc. A structure in which two or more types of porous membranes are laminated can also be used. . Among them, a porous membrane made of polyolefin is preferable because it is excellent in the short circuit preventing effect and can improve the safety of the battery by the shutdown effect.
  • magnesium ions move from the positive electrode member 10 through the electrolytic solution 12 to the negative electrode member 11 during charging, as shown in the conceptual diagram in FIG.
  • electrical energy is converted into chemical energy and stored.
  • the magnesium ions return from the negative electrode member 11 to the positive electrode member 10 through the electrolytic solution 12 to generate electrical energy.
  • a battery including the magnesium secondary battery of the present disclosure can be mentioned broadly, and a more specific secondary As the battery, in addition to the magnesium secondary battery, an air battery and a fuel cell can be mentioned.
  • the magnesium secondary battery (or electrochemical device) of the present disclosure is, for example, a laptop personal computer, a PDA (personal digital assistant), a mobile phone, a smart phone, a cordless telephone master or slave, a video movie, a digital still camera Electronic books, electronic dictionaries, portable music players, radios, headphones, game consoles, navigation systems, memory cards, cardiac pacemakers, hearing aids, power tools, electric shavers, refrigerators, air conditioners, television receivers, stereos, water heaters, Microwave ovens, dishwashers, washing machines, dryers, lighting devices, toys, medical devices, IoT devices and IoT terminals, robots, road conditioners, traffic lights, railway cars, golf carts, electric carts, electric cars (including hybrid cars Driving etc) It can be power or used as an auxiliary power source.
  • a converter that converts power into driving force by supplying power is generally a motor.
  • the control device (control unit) that performs information processing related to vehicle control includes a control device that performs battery remaining amount display based on information regarding the remaining amount of the magnesium secondary battery.
  • a magnesium secondary battery can also be used in the electrical storage apparatus in what is called a smart grid.
  • Such a power storage device can not only supply power but also store power by receiving supply of power from another power source.
  • power sources for example, thermal power generation, nuclear power generation, hydroelectric power generation, solar cells, wind power generation, geothermal power generation, fuel cells (including biofuel cells) and the like can be used.
  • a secondary battery a control unit (control unit) that performs control regarding the secondary battery, and a secondary battery in a battery pack having an outer package including the secondary battery, including the above-described various preferable embodiments and configurations of the preferred embodiments
  • a magnesium secondary battery can be applied.
  • the control means controls, for example, charge and discharge, overdischarge, or overcharge related to the secondary battery.
  • the magnesium secondary battery of the present disclosure including the various preferred embodiments and configurations described above can be applied to a secondary battery in an electronic device that receives power supply from the secondary battery.
  • a secondary in an electric vehicle having a conversion device that receives supply of electric power from a secondary battery and converts it into driving force of the vehicle, and a control device (control unit) that performs information processing related to vehicle control based on information on the secondary battery
  • the magnesium secondary battery of the present disclosure including the various preferred embodiments and configurations described above can be applied to the battery.
  • the conversion device typically receives power supplied from a magnesium secondary battery to drive a motor to generate a driving force. Regenerative energy can also be used to drive the motor.
  • the control device (control unit) performs information processing related to vehicle control, for example, based on the battery remaining amount of the magnesium secondary battery.
  • the electric vehicle includes, for example, so-called hybrid vehicles as well as electric vehicles, electric motorcycles, electric bicycles, railway vehicles and the like.
  • the present disclosure including various preferred forms and configurations described above for a secondary battery in a power system configured to receive supply of power from the secondary battery and / or supply power from the power source to the secondary battery.
  • the magnesium secondary battery can be applied.
  • This power system may be any power system as long as it uses approximately power, and also includes a mere power device.
  • the power system includes, for example, a smart grid, a home energy management system (HEMS), a vehicle, and the like, and can also store power.
  • HEMS home energy management system
  • the magnesium secondary battery of the present disclosure including the various preferred embodiments and configurations described above for the secondary battery in a power storage power supply configured to be connected to an electronic device having a secondary battery and to which power is supplied. Can be applied.
  • the power storage power source can be basically used in any power system or power device regardless of the application of the power source, but it can be used, for example, in a smart grid.
  • the electrolytic solution and the like of the present disclosure can also be used for capacitors, various sensors, magnesium ion filters, and the like.
  • the electrolytic solution or the like of the present disclosure including the preferred embodiment and configuration described above can be used as a plating bath. That is, the electrolytic solution or the like of the present disclosure including the preferred embodiment and configuration described above is used as a plating bath, and a plate-like or rod-like magnesium metal single body is used as an anode (counter electrode), for example.
  • a plate-like or rod-like magnesium metal single body is used as an anode (counter electrode), for example.
  • platinum (Pt) or a platinum alloy, nickel (Ni) or nickel alloy, stainless steel, or a current collector material for a negative electrode may be used as the material to be plated.
  • Example 1 is an electrolytic solution according to the first to fourth aspects of the present disclosure, a magnesium secondary battery according to the first to fourth aspects of the present disclosure, and production of the electrolytic solution of the present disclosure On the way.
  • the magnesium secondary battery of Example 1 is a magnesium secondary battery provided with a positive electrode containing sulfur or a sulfur compound, a negative electrode containing magnesium or a magnesium compound, and an electrolytic solution. Specifically, as shown in a schematic exploded view of the magnesium secondary battery of Example 1 in FIG. 1, the magnesium secondary battery of Example 1 is constituted of, for example, a coin battery 20 of the CR 2016 type.
  • a positive electrode member 23 provided with at least a positive electrode active material layer 23B (specifically, in Example 1, a positive electrode member 23 provided with a positive electrode current collector 23A and a positive electrode active material layer 23B); A separator 24 disposed opposite to the positive electrode member 23 (more specifically, the positive electrode active material layer 23B); A negative electrode member 25 containing magnesium or a magnesium compound disposed opposite to the separator 24; A solvent comprising sulfone, and an electrolytic solution comprising magnesium salt dissolved in the solvent, It is a magnesium secondary battery equipped with
  • the sulfone comprises an alkyl sulfone represented by R 1 R 2 SO 2 (wherein R 1 and R 2 each independently represent an alkyl group) or an alkyl sulfone derivative.
  • R 1 and R 2 each independently represent an alkyl group
  • the magnesium salt contains magnesium chloride (MgCl 2 )
  • the sulfone constituting the electrolyte contains ethyl-n-propylsulfone (EnPS).
  • the constituent members of the magnesium secondary battery are as follows.
  • Electrolyte component MgCl 2 (anhydride): Sigma-Aldrich ethyl normal propyl sulfone (EnPS) : Dehydration specification for battery for Toyama Pharmaceutical Co., Ltd./Separator constituent material: Glass filter GC50 made by Advantech Co., Ltd.
  • an electrolytic solution (MgCl 2 -EnPS) was prepared as follows.
  • EnPS which performed the removal operation of the impurity was used as EnPS.
  • Measurement, weighing and mixing operation of reagents for electrolyte preparation were carried out in a glove box (argon gas atmosphere, dew point is ⁇ 80 ° C. to ⁇ 90 ° C.).
  • the magnesium salt was pulverized, mixed with a solvent, and heated and stirred to produce an electrolytic solution of Example 1.
  • MgCl 2 (anhydride) was weighed and ground using a rattan mortar. Subsequently, MgCl 2 and EnPS were mixed so as to obtain a desired Mg molar ratio, and various electrolytes of Example 1 shown in Table 2 below and Comparative Example 1 were heated and stirred at 140 ° C. for 4 hours.
  • the magnesium secondary battery (coin battery 20, CR2016 type) of Example 1 can be manufactured based on the following method. That is, placing the gasket 22 in a coin battery can 21, (positive electrode active material layer 23B made of nickel metal gauze (made of mesh) positive electrode current collector 23A and sulfur S 8) positive electrode member 23, the separator 24, the diameter of 15 mm Mg After laminating the negative electrode member 25 consisting of a plate, the spacer 26 consisting of a stainless steel plate having a thickness of 0.5 mm, and the coin battery lid 27 in this order, the coin battery can 21 was crimped and sealed. The spacer 26 was spot-welded to the coin battery cover 27 in advance.
  • the electrolytic solution of Example 1 is contained in the separator (manufactured by Advantec Co., Ltd., glass filter GC50) 24.
  • the voltage range is 0.7 to 2.5 volts
  • the current density is a constant current of 0.1 milliamperes
  • charging is stopped when it reaches 2.5 volts
  • 0.7 is discharged.
  • the discharge was stopped when it reached to the bolt.
  • charge and discharge could be performed without any problem.
  • cycle characteristics superior to those of the magnesium secondary battery of Comparative Example 1 using the electrolytic solution of Comparative Example 1 were exhibited.
  • FIG. 2A The results of Raman spectroscopic measurement of the electrolytes of Example 1A, Example 1B, Example 1C and Comparative Example 1 are shown in FIG. 2A.
  • the change in peak position or intensity is Based on the least peak value of the Raman spectrum intensity [specifically, in the above example and comparative example, the peak value of the Raman spectrum intensity appearing first at a Raman shift of 1000 cm -1 or less (more specifically , Based on the value of the Raman shift RS 0 : 982 cm -1 ), the normalization of the Raman spectrum intensity of the electrolytic solution and the Raman spectrum intensity of the solvent is performed.
  • the entire Raman spectrum intensity of the electrolyte and the entire Raman spectrum intensity of the solvent are corrected (normalized) so that the Raman spectrum intensity of the electrolyte and the Raman spectrum intensity of the solvent at the Raman shift RS 0 982 cm -1 become equal. ).
  • the value of the Raman shift value RS 1 of the solvent having no interaction with the electrolyte which was determined based on the method described above, was 1125 cm ⁇ 1 and 1130 cm ⁇ 1 .
  • the value RS 2 of the Raman shift of the solvent strongly interacting with the electrolyte (or interacting with the electrolyte) was 1149 cm ⁇ 1 .
  • the Raman spectrum intensity of which the change in peak position or intensity is least Raman spectrum intensity of the electrolyte and Raman spectrum intensity of the solvent based on the peak value (specifically, in the example, based on the peak value of the Raman spectrum intensity appearing first with a Raman shift of 1000 cm -1 or less)
  • the Raman spectrum intensity of the solvent alone at the value RS 1 of the solvent is I 11
  • the Raman spectrum intensity of the electrolyte solution is I 12
  • the Mg molar ratio is 4 or less, preferably less than 4, so that the solvent in a state in which interaction with the electrolyte is weak (or in a state without interaction with the electrolyte) is reduced.
  • a magnesium secondary battery having excellent characteristics can be provided by using the electrolytic solution of Example 1, and excellent characteristics can be obtained by using the electrolytic solution of Example 1 having a Mg molar ratio of less than 4.
  • a magnesium secondary battery can be provided.
  • the relationship between the free solvent (EnPS) and the solvent (EnPS) strongly interacting with the electrolyte can be represented by the following formula (A).
  • the peak area (area of the peak of Raman spectrum intensity) of free EnPS can be represented by the following formula (B).
  • Ie, x-axis and C s / C Mg is Mg molar ratio, by plotting the I f / C Mg as y-axis, the x-intercept, interacting strongly with dissolved magnesium salt (or dissolved).
  • the abundance ratio n to magnesium of the solvent molecule (interacting with the magnesium salt) can be estimated.
  • the existence ratio of the solvent molecule strongly interacting with the dissolved magnesium salt (or interacting with the dissolved magnesium salt) to magnesium is It is 0.5 or more. From this result, it is found that the free solvent is about 1 ⁇ 2 ( ⁇ 0.5), about 2 ⁇ 3 (7 0.67), in the electrolytic solution when the Mg molar ratio is 2, 3 and 4. There are about 3/4 ( ⁇ 0.75). Accordingly, in other words, it is preferable to use an electrolytic solution in which the ratio of the solvent having no interaction with the electrolyte to the total solvent is 3/4 or less.
  • the electrolytic solution containing few free solvents will have less elution of the positive electrode active material (specifically, in Example 1, sulfur), but it must have precipitation dissolution activity (precipitation dissolution reaction) of magnesium.
  • the positive electrode active material specifically, in Example 1, sulfur
  • a platinum (Pt) working electrode is used, the counter and reference electrodes are made of magnesium (Mg), the measurement range is -1.5 to 2.0 volts, and the scan speed is 5 millivolts. It measured by / second. That is, the measurement in the first cycle starts from the open circuit state (OCV), first reduces the potential of the working electrode with respect to the potential of the reference electrode to about -1.5 volts to the reduction side and then to the oxidation side 2 The voltage was changed in the order of OCV ⁇ approximately ⁇ 1.5 volts ⁇ approximately +2.0 volts ⁇ OCV so as to raise to approximately 0 volts and finally return to OCV.
  • OCV open circuit state
  • the ion conductivity at room temperature is 1.1 ⁇ 10 ⁇ 5 (S / cm), and the ion conductivity at 75 ° C. is 2.1 ⁇ 10 ⁇ 4 (S / Cm).
  • the Mg molar ratio is defined, and thus the interaction with the electrolyte is weak (or the interaction with the electrolyte is Solvent) is reduced, the ratio of Raman spectral intensities in Raman spectroscopy is defined, and the presence of solvent molecules strongly interacting with the dissolved magnesium salt relative to the magnesium salt Since the ratio (the ratio of the solvent having no interaction with the electrolyte to the total solvent) is defined, and the Mg molar ratio is defined, there is no interaction with the electrolyte constituting the electrolyte (or alternatively (In a state where the interaction with the electrolyte is weak), the capacity deterioration due to the elution of the positive electrode active material (specifically, sulfur) is reduced, and excellent cycle characteristics are obtained. It is possible to provide a magnesium secondary battery.
  • the preparation of the electrolytic solution can also be performed by the following method.
  • the electrolytic solution thus obtained also showed the same performance as the electrolytic solution obtained by the method of grinding the magnesium salt described above, mixing with a solvent, heating and stirring.
  • Example 2 is a modification of Example 1.
  • the electrochemical device of Example 2 comprises a capacitor as shown in a schematic cross-sectional view in FIG. 4, and the positive electrode 31 and the negative electrode 32 face each other through the separator 33 impregnated with the electrolytic solution of Example 1 Are arranged.
  • Reference numerals 35 and 36 indicate current collectors, and reference numeral 37 indicates a gasket.
  • the positive electrode 31 and the negative electrode 32 are formed of the positive electrode member and the negative electrode member of the first embodiment.
  • the electrolytic solution of Example 1 is contained in the separator 33.
  • the electrochemical device of Example 2 consists of an air battery, as shown in a conceptual diagram in FIG.
  • the air battery includes, for example, an oxygen-selective permeable film 47 which is hard to transmit water vapor and selectively transmits oxygen, an air electrode side current collector 44 made of a conductive porous material, and the air electrode side current collector 44 And a porous diffusion layer 46 made of a conductive material and disposed between the porous positive electrode 41 and the porous positive electrode 41, a porous positive electrode 41 containing a conductive material and a catalyst material, a separator that hardly passes water vapor, and an electrolyte (or an electrolyte (Solid electrolyte included) 43, a negative electrode member 42 for releasing magnesium ions, a negative electrode side current collector 45, and an exterior body 48 in which these layers are accommodated.
  • the electrolyte comprises the electrolyte of Example 1.
  • the oxygen 52 in the air (atmosphere) 51 is selectively permeated by the oxygen selective permeable film 47, passes through the air electrode side current collector 44 made of a porous material, is diffused by the diffusion layer 46, and the porous positive electrode 41 Supplied to The progress of oxygen transmitted through the oxygen selective permeable film 47 is partially blocked by the air electrode side current collector 44, but the oxygen having passed through the air electrode side current collector 44 is diffused and diffused by the diffusion layer 46.
  • the air can be efficiently distributed to the entire porous positive electrode 41, and the supply of oxygen to the entire surface of the porous positive electrode 41 is not inhibited by the air electrode side current collector 44.
  • the electrochemical device of Example 2 comprises a fuel cell, as shown in a conceptual diagram in FIG.
  • This fuel cell includes, for example, a positive electrode member 61, a positive electrode electrolyte 62, a positive electrode electrolyte transport pump 63, a fuel flow path 64, a positive electrode electrolyte storage container 65, a negative member 71, a negative electrode electrolyte 72, and a negative electrode.
  • An electrolyte solution transport pump 73, a fuel flow path 74, an electrolyte solution storage container 75 for the negative electrode, and an ion exchange membrane 66 are provided.
  • the positive electrode electrolyte 62 continuously or intermittently flows (circulates) through the positive electrode electrolyte storage container 65 and the positive electrode electrolyte transfer pump 63, and the fuel flow In the passage 74, the negative electrode electrolyte 72 continuously or intermittently flows (circulates) through the negative electrode electrolyte storage container 75 and the negative electrode electrolyte transport pump 73. Power generation is performed with the negative electrode member 71.
  • the electrolytic solution 62 for positive electrode one obtained by adding the positive electrode active material to the electrolytic solution of Example 1 can be used, and as the electrolytic solution 72 for negative electrode, one using the negative electrode active material added to the electrolytic solution of Example 1 is used. be able to.
  • the magnesium secondary battery of the present disclosure described in the first embodiment is a machine, an apparatus, an apparatus, a system (a plurality of machines, an apparatus, an apparatus, and The present invention can be applied to a collection of devices and the like without particular limitation.
  • the magnesium secondary battery (specifically, a magnesium-sulfur secondary battery) used as a power source may be a main power source (a power source used preferentially) or an auxiliary power source (in place of the main power source) Or, it may be a power supply used by switching from the main power supply).
  • the main power source is not limited to the magnesium secondary battery.
  • Power storage systems such as TV systems, home energy servers (home power storage devices), power supply systems; power storage units and backup power supplies; electric vehicles, electric bikes, electric bicycles, electric vehicles such as Segway (registered trademark); aircraft and ships
  • a power driving force conversion device specifically, for example, a power motor
  • the magnesium secondary battery of the present disclosure is applied to a battery pack, an electric vehicle, an electric power storage system, an electric power supply system, an electric tool, an electronic device, an electric device and the like.
  • the battery pack is a power source using the magnesium secondary battery of the present disclosure, and is a so-called assembled battery or the like.
  • the electric vehicle is a vehicle that operates (travels) using the magnesium secondary battery of the present disclosure as a driving power source, and may be an automobile (hybrid vehicle or the like) that is provided with a driving source other than the secondary battery.
  • the power storage system (power supply system) is a system using the magnesium secondary battery of the present disclosure as a power storage source.
  • the electric power tool is a tool in which a movable portion (for example, a drill or the like) moves using the magnesium secondary battery of the present disclosure as a power supply for driving.
  • the electronic device and the electric device are devices that exhibit various functions as a power supply (power supply source) for operating the magnesium secondary battery of the present disclosure.
  • FIG. 1 A schematic cross-sectional view of a cylindrical magnesium secondary battery 100 is shown in FIG.
  • the electrode structure 121 and the pair of insulating plates 112 and 113 are accommodated in the substantially hollow cylindrical electrode structure accommodating member 111.
  • the electrode structure 121 can be produced, for example, by laminating the positive electrode member 122 and the negative electrode member 124 via the separator 126 to obtain an electrode structure, and then winding the electrode structure.
  • the electrode structure storage member (battery can) 111 has a hollow structure in which one end is closed and the other end is opened, and is made of iron (Fe), aluminum (Al) or the like.
  • the surface of the electrode structure storage member 111 may be plated with nickel (Ni) or the like.
  • the pair of insulating plates 112 and 113 sandwich the electrode structure 121 and is arranged to extend perpendicularly to the winding circumferential surface of the electrode structure 121.
  • a battery cover 114, a safety valve mechanism 115 and a thermal resistance element (PTC element, positive temperature coefficient element) 116 are crimped via a gasket 117, whereby the electrode The structure storage member 111 is sealed.
  • the battery cover 114 is made of, for example, the same material as the electrode structure storage member 111.
  • the safety valve mechanism 115 and the thermal resistance element 116 are provided inside the battery cover 114, and the safety valve mechanism 115 is electrically connected to the battery cover 114 via the thermal resistance element 116.
  • the disc plate 115A is reversed when the internal pressure becomes equal to or higher than a predetermined value due to internal short circuit or external heating. Then, the electrical connection between the battery cover 114 and the electrode structure 121 is cut off. In order to prevent abnormal heat generation caused by a large current, the resistance of the heat sensitive resistance element 116 increases with the temperature rise.
  • the gasket 117 is made of, for example, an insulating material. Asphalt etc. may be applied to the surface of the gasket 117.
  • the positive electrode lead portion 123 made of a conductive material such as aluminum is connected to the positive electrode member 122. Specifically, the positive electrode lead portion 123 is attached to the positive electrode current collector.
  • a negative electrode lead portion 125 made of a conductive material such as copper is connected to the negative electrode member 124. Specifically, the negative electrode lead portion 125 is attached to the negative electrode current collector.
  • the negative electrode lead portion 125 is welded to the electrode structure storage member 111 and is electrically connected to the electrode structure storage member 111.
  • the positive electrode lead portion 123 is welded to the safety valve mechanism 115 and electrically connected to the battery lid 114.
  • the negative electrode lead portion 125 is at one place (the outermost periphery of the wound electrode assembly), but at two places (the outermost periphery and the outermost periphery of the wound electrode assembly) It may be provided on the inner circumference).
  • the electrode structure 121 includes a positive electrode member 122 having a positive electrode active material layer formed on the positive electrode current collector (specifically, on both sides of the positive electrode current collector), and on the negative electrode current collector (specifically, And the negative electrode member 124 in which the negative electrode active material layer was formed on both surfaces of the negative electrode current collector is laminated via the separator 126.
  • the positive electrode active material layer is not formed in the region of the positive electrode current collector to which the positive electrode lead portion 123 is attached, and the negative electrode active material layer is not formed in the region of the negative electrode current collector to which the negative electrode lead portion 125 is attached.
  • the specifications of the magnesium secondary battery 100 are exemplified in Table 6 below, but are not limited thereto.
  • the magnesium secondary battery 100 can be manufactured, for example, based on the following procedure.
  • a positive electrode active material layer is formed on both sides of the positive electrode current collector, and a negative electrode active material layer is formed on both sides of the negative electrode current collector.
  • the positive electrode lead portion 123 is attached to the positive electrode current collector using a welding method or the like.
  • the negative electrode lead portion 125 is attached to the negative electrode current collector using a welding method or the like.
  • the positive electrode member 122 and the negative electrode member 124 are laminated through a separator 126 made of a microporous polyethylene film with a thickness of 20 ⁇ m and wound (more specifically, the positive electrode member 122 / separator 126 / negative electrode
  • a protective tape (not shown) is attached to the outermost periphery.
  • the center pin 118 is inserted into the center of the electrode structure 121.
  • the electrode structure 121 is housed inside the electrode structure housing member (battery can) 111 while sandwiching the electrode structure 121 between the pair of insulating plates 112 and 113.
  • the front end portion of the positive electrode lead portion 123 is attached to the safety valve mechanism 115 and the front end portion of the negative electrode lead portion 125 is attached to the electrode structure storage member 111 using a welding method or the like.
  • the electrolyte solution of Example 1 is injected based on the pressure reduction method to impregnate the separator 126 with the electrolyte solution.
  • the battery cover 114, the safety valve mechanism 115, and the heat sensitive resistance element 116 are crimped to the open end of the electrode structure storage member 111 via the gasket 117.
  • FIG. 1 A schematic exploded perspective view of a magnesium secondary battery is shown in FIG.
  • the same electrode structure 221 as that described above is basically housed inside the exterior member 200 made of a laminate film.
  • the electrode structure 221 can be manufactured by winding the laminated structure after laminating the positive electrode member and the negative electrode member via the separator and the electrolyte layer.
  • the positive electrode lead portion 223 is attached to the positive electrode member, and the negative electrode lead portion 225 is attached to the negative electrode member.
  • the outermost periphery of the electrode structure 221 is protected by a protective tape.
  • the positive electrode lead portion 223 and the negative electrode lead portion 225 protrude from the inside to the outside of the package member 200 in the same direction.
  • the positive electrode lead portion 223 is formed of a conductive material such as aluminum.
  • the negative electrode lead portion 225 is formed of a conductive material such as copper, nickel, stainless steel or the like.
  • the exterior member 200 is a single sheet of film foldable in the direction of the arrow R shown in FIG. 8, and a recess (emboss) for housing the electrode structure 221 is provided in a part of the exterior member 200.
  • the exterior member 200 is, for example, a laminate film in which a fusion bonding layer, a metal layer, and a surface protective layer are laminated in this order.
  • the package member 200 may be a laminate of two laminated films with an adhesive or the like.
  • the fusion layer is made of, for example, a film of polyethylene, polypropylene or the like.
  • the metal layer is made of, for example, an aluminum foil or the like.
  • the surface protective layer is made of, for example, nylon, polyethylene terephthalate or the like.
  • the exterior member 200 is preferably an aluminum laminate film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order.
  • the exterior member 200 may be a laminate film having another laminated structure, a polymer film such as polypropylene, or a metal film.
  • a moisture resistant aluminum laminate film (total thickness) in which a nylon film (thickness 30 ⁇ m), an aluminum foil (thickness 40 ⁇ m), and a non-oriented polypropylene film (thickness 30 ⁇ m) are laminated in this order from the outside 100 ⁇ m).
  • An adhesive film 201 is inserted between the exterior member 200 and the positive electrode lead portion 223 and between the exterior member 200 and the negative electrode lead portion 225 in order to prevent the intrusion of the outside air.
  • the adhesive film 201 is made of a material having adhesiveness to the positive electrode lead portion 223 and the negative electrode lead portion 225, for example, a polyolefin resin or the like, more specifically, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene or modified polypropylene. .
  • the battery pack is a simple battery pack (so-called soft pack) using one of the magnesium secondary batteries of the present disclosure, and is mounted on, for example, an electronic device represented by a smartphone.
  • it comprises a battery assembly composed of six magnesium secondary batteries of the present disclosure connected in two parallel three series.
  • the connection type of the magnesium secondary battery may be in series, in parallel, or a combination of both.
  • the battery pack includes a cell (assembled battery) 1001, an exterior member, a switch unit 1021, a current detection resistor 1014, a temperature detection element 1016, and a control unit 1010.
  • the switch unit 1021 includes a charge control switch 1022 and a discharge control switch 1024.
  • the battery pack includes a positive electrode terminal 1031 and a negative electrode terminal 1032, and during charging, the positive electrode terminal 1031 and the negative electrode terminal 1032 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, to perform charging.
  • the positive electrode terminal 1031 and the negative electrode terminal 1032 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.
  • the cell 1001 is configured by connecting a plurality of magnesium secondary batteries 1002 of the present disclosure in series and / or in parallel.
  • FIG. 9 shows the case where six magnesium secondary batteries 1002 are connected in two parallel three series (2P3S), but in addition, like p parallel q series (where p and q are integers) Any connection method may be used.
  • the switch unit 1021 includes a charge control switch 1022 and a diode 1023, and a discharge control switch 1024 and a diode 1025, and is controlled by the control unit 1010.
  • the diode 1023 has a reverse direction to the charge current flowing from the positive electrode terminal 1031 to the cell 1001 and a forward direction to the discharge current flowing from the negative electrode terminal 1032 to the cell 1001.
  • the diode 1025 has a forward direction with respect to the charge current and a reverse direction with respect to the discharge current.
  • the switch portion is provided on the plus (+) side in the example, it may be provided on the minus ( ⁇ ) side.
  • the charge control switch 1022 is closed when the battery voltage becomes the overcharge detection voltage, and is controlled by the control unit 1010 so that the charge current does not flow in the current path of the cell 1001. After the charge control switch 1022 is closed, only discharge can be performed through the diode 1023.
  • the control unit 1010 is controlled to be closed and to cut off the charging current flowing in the current path of the cell 1001.
  • the discharge control switch 1024 is closed when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 1010 so that the discharge current does not flow in the current path of the cell 1001. After the discharge control switch 1024 is closed, only charging can be performed through the diode 1025.
  • the control unit 1010 is controlled to be closed and to interrupt the discharge current flowing in the current path of the cell 1001.
  • the temperature detection element 1016 is, for example, a thermistor, and is provided in the vicinity of the cell 1001.
  • the temperature measurement unit 1015 measures the temperature of the cell 1001 using the temperature detection element 1016 and sends the measurement result to the control unit 1010.
  • the voltage measuring unit 1012 measures the voltage of the cell 1001 and the voltage of each of the magnesium secondary batteries 1002 that constitute the cell 1001, A / D converts the measurement result, and sends it to the control unit 1010.
  • the current measurement unit 1013 measures the current using the current detection resistor 1014, and sends the measurement result to the control unit 1010.
  • the switch control unit 1020 controls the charge control switch 1022 and the discharge control switch 1024 of the switch unit 1021 based on the voltage and current sent from the voltage measurement unit 1012 and the current measurement unit 1013.
  • the switch control unit 1020 controls the switch unit 1021 when any voltage of the magnesium secondary battery 1002 falls below the overcharge detection voltage or the overdischarge detection voltage, or when a large current rapidly flows. By sending a signal, overcharge and overdischarge, and over current charge and discharge are prevented.
  • the charge control switch 1022 and the discharge control switch 1024 can be composed of, for example, a semiconductor switch such as a MOSFET. In this case, diodes 1023 and 1025 are configured by parasitic diodes of the MOSFETs.
  • the switch control unit 1020 supplies the control signal DO and the control signal CO to the gate portions of the charge control switch 1022 and the discharge control switch 1024.
  • the charge control switch 1022 and the discharge control switch 1024 are turned on by the gate potential which is lower than the source potential by a predetermined value or more. That is, in the normal charge and discharge operation, the control signal CO and the control signal DO are set to the low level, and the charge control switch 1022 and the discharge control switch 1024 are brought into conduction. Then, for example, in the case of overcharge or overdischarge, the control signal CO and the control signal DO are set to the high level, and the charge control switch 1022 and the discharge control switch 1024 are closed.
  • the memory 1011 is formed of, for example, an EPROM (Erasable Programmable Read Only Memory) which is a non-volatile memory.
  • the memory 1011 stores in advance the numerical value calculated by the control unit 1010, the internal resistance value of the magnesium secondary battery in the initial state of each magnesium secondary battery 1002 measured at the stage of the manufacturing process, and the like. And can be rewritten as appropriate. Further, by storing the full charge capacity of the magnesium secondary battery 1002, for example, the remaining capacity can be calculated together with the control unit 1010.
  • EPROM Erasable Programmable Read Only Memory
  • the temperature measurement unit 1015 measures the temperature using the temperature detection element 1016, performs charge / discharge control at the time of abnormal heat generation, and performs correction in calculation of the remaining capacity.
  • FIG. 10A is a block diagram showing a configuration of an electric-powered vehicle such as a hybrid car which is an example of the electric-powered vehicle.
  • the motor-driven vehicle includes a control unit 2001, various sensors 2002, a power supply 2003, an engine 2010, a generator 2011, inverters 2012 and 2013, a driving motor 2014, a differential gear 2015, and the like inside a metal case 2000.
  • a transmission 2016 and a clutch 2017 are provided.
  • the electric vehicle includes, for example, a front wheel drive shaft 2021, a front wheel 2022, a rear wheel drive shaft 2023, and a rear wheel 2024 connected to the differential device 2015 and the transmission 2016.
  • the electric vehicle can travel, for example, using either the engine 2010 or the motor 2014 as a drive source.
  • the engine 2010 is a main power source, such as a gasoline engine.
  • the driving force (rotational force) of the engine 2010 is transmitted to the front wheel 2022 or the rear wheel 2024 via, for example, the differential device 2015 as a driving unit, the transmission 2016, and the clutch 2017.
  • the rotational force of the engine 2010 is also transmitted to the generator 2011, and the generator 2011 generates alternating current power using the rotational force, and the alternating current power is converted to direct current power via the inverter 2013 and stored in the power supply 2003 .
  • the motor 2014 which is a conversion unit is used as a motive power source
  • the electric power (DC power) supplied from the power source 2003 is converted into AC power via the inverter 2012, and the motor 2014 is driven using AC power.
  • the driving force (rotational force) converted from the electric power by the motor 2014 is transmitted to the front wheel 2022 or the rear wheel 2024 via, for example, the differential device 2015 as a driving unit, the transmission 2016, and the clutch 2017.
  • the resistance during deceleration is transmitted to the motor 2014 as a rotational force, and the rotational force may be used to cause the motor 2014 to generate AC power.
  • AC power is converted to DC power via inverter 2012, and DC regenerative power is stored in power supply 2003.
  • the control unit 2001 controls the operation of the entire electric vehicle, and includes, for example, a CPU.
  • the power source 2003 includes one or more magnesium secondary batteries (not shown) described in the first embodiment.
  • the power supply 2003 may be connected to an external power supply, and may be configured to store power by receiving power supply from the external power supply.
  • the various sensors 2002 are used, for example, to control the rotational speed of the engine 2010 and to control the opening degree (throttle opening degree) of a throttle valve (not shown).
  • the various sensors 2002 include, for example, a speed sensor, an acceleration sensor, an engine rotational speed sensor, and the like.
  • the electric vehicle may be a vehicle (electric vehicle) that operates only using the power supply 2003 and the motor 2014 without using the engine 2010.
  • the power storage system includes, for example, a control unit 3001, a power supply 3002, a smart meter 3003, and a power hub 3004 inside a house 3000 such as a home or a commercial building.
  • the power supply 3002 is connected to, for example, an electric device (electronic device) 3010 installed inside the house 3000, and can be connected to an electric vehicle 3011 stopped outside the house 3000.
  • the power supply 3002 is connected to, for example, a private generator 3021 installed in a house 3000 via a power hub 3004, and can be connected to an external centralized power system 3022 via a smart meter 3003 and a power hub 3004. is there.
  • the electrical device (electronic device) 3010 includes, for example, one or more home appliances. As a household appliance, a refrigerator, an air-conditioner, a television receiver, a water heater etc. can be mentioned, for example.
  • the private generator 3021 is configured of, for example, a solar power generator, a wind power generator, or the like.
  • Examples of the electric vehicle 3011 include an electric car, a hybrid car, an electric motorcycle, an electric bicycle, Segway (registered trademark), and the like.
  • a centralized power system 3022 a commercial power source, a power generation device, a power transmission network, a smart grid (next generation power transmission network) can be mentioned, and also, for example, a thermal power plant, a nuclear power plant, a hydroelectric power plant, a wind power plant
  • various solar cells, fuel cells, wind power generators, micro-hydro power generators, geothermal power generators, etc. can be exemplified as the power generators provided in the centralized power grid 3022. It is not limited to these.
  • the control unit 3001 controls the operation of the entire power storage system (including the use state of the power supply 3002), and includes, for example, a CPU.
  • the power supply 3002 includes one or more magnesium secondary batteries (not shown) described in the first embodiment.
  • the smart meter 3003 is, for example, a network compatible power meter installed in a house 3000 on the power demand side, and can communicate with the power supply side. The smart meter 3003 can perform efficient and stable energy supply by controlling the balance of supply and demand in the house 3000 while communicating with the outside, for example.
  • the power storage system for example, power is stored in the power supply 3002 from the centralized power system 3022 which is an external power supply via the smart meter 3003 and the power hub 3004, and from an independent generator 3021 to the power hub 3004. Power is then stored in the power supply 3002.
  • the electric power stored in the power supply 3002 is supplied to the electric device (electronic device) 3010 and the electric vehicle 3011 according to the instruction of the control unit 3001, so that the electric device (electronic device) 3010 can be operated and The vehicle 3011 can be charged.
  • the power storage system is a system that enables storage and supply of power in the house 3000 using the power supply 3002.
  • the power stored in the power supply 3002 is arbitrarily available. Therefore, for example, power can be stored in the power supply 3002 from the centralized power system 3022 at midnight, at which the electricity charge is inexpensive, and the power stored in the power supply 3002 can be used during the day when the electricity charge is high.
  • the power storage system described above may be installed for each household (one household), or may be installed for each household (plural households).
  • the power tool is, for example, a power drill, and includes a control unit 4001 and a power supply 4002 inside a tool main body 4000 made of a plastic material or the like.
  • a drill portion 4003 which is a movable portion is rotatably attached to the tool main body 4000.
  • the control unit 4001 controls the operation of the entire electric power tool (including the use state of the power supply 4002), and includes, for example, a CPU.
  • the power supply 4002 includes one or more magnesium secondary batteries (not shown) described in the first embodiment.
  • the control unit 4001 supplies power from the power supply 4002 to the drill unit 4003 according to the operation of the operation switch (not shown).
  • the composition of the electrolytic solution described in the examples, the raw materials used for the production, the production method, the production conditions, the characteristics of the electrolytic solution, the configuration and structure of the battery including the magnesium secondary battery and the electrochemical device are examples. And may be changed as appropriate.
  • the electrolyte solution of the present disclosure may be mixed with an organic polymer (eg, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride (PVdF)) and used as a gel electrolyte.
  • an organic polymer eg, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride (PVdF)
  • the electrolyte described in Example 1 can be used as a plating bath for electroplating magnesium. That is, the electrolytic solution of the present disclosure including the preferred embodiment and configuration described above is used as a plating bath, and a plate-like or rod-like magnesium metal single body is used as an anode (counter electrode), for example.
  • a plate-like or rod-like magnesium metal single body is used as an anode (counter electrode), for example.
  • As the material to be plated for example, platinum (Pt) or a platinum alloy, nickel (Ni) or a nickel alloy, stainless steel, or a current collector material for a negative electrode may be used.
  • the magnesium salt-A and magnesium salt-B described above can be exemplified as the magnesium salt constituting the plating bath for electroplating magnesium.
  • Such a plating bath is Dissolve the magnesium salt in a low boiling point solvent in which the magnesium salt is soluble, then After dissolving sulfone (specifically, the sulfone described above) in a solution in which a magnesium salt is dissolved in a low boiling point solvent, It can be obtained by removing the low boiling point solvent from the solution in which the sulfone is dissolved by heating under reduced pressure.
  • sulfone specifically, the sulfone described above
  • any solvent having a boiling point lower than that of the selected sulfone may basically be used, but It is preferred to use an alcohol.
  • the above-described additive may be contained in the plating bath described above, and the addition of such an additive can improve the ion conductivity of the plating bath. Furthermore, it can also be made into the form containing the various nonpolar solvent mentioned above. That is, a nonpolar solvent may be mixed with the plating bath. Nonpolar solvents function as a kind of diluent.
  • the negative electrode in an electrochemical device can also be manufactured by the following method. That is, a Mg electrolytic solution (Mg-EnPS) having Mg molar ratio of MgCl 2 and EnPS (ethyl-n-propyl sulfone) is prepared, and this Mg electrolytic solution is used to form a Cu foil on the basis of an electrolytic plating method. Mg metal is deposited to form an Mg plated layer on a Cu foil as an active material layer in the negative electrode.
  • Mg-EnPS Mg electrolytic solution having Mg molar ratio of MgCl 2 and EnPS (ethyl-n-propyl sulfone)
  • Mg-EnPS Mg electrolytic solution having Mg molar ratio of MgCl 2 and EnPS (ethyl-n-propyl sulfone) is prepared, and this Mg electrolytic solution is used to form a Cu foil on the basis of an electrolytic plating method.
  • Mg metal is deposited to form
  • Electrolyte solution First aspect >> A solvent comprising sulfone, and a magnesium salt dissolved in the solvent; The value of (mole number of sulfone) / (mole number of magnesium constituting magnesium salt) value (molar ratio of Mg) is 4 or less, so that the solvent in the state of weak interaction with the electrolyte is reduced Electrolyte solution.
  • Electrolyte solution Second aspect >> An electrolyte comprising a solvent comprising sulfone and a magnesium salt dissolved in the solvent, In Raman spectroscopy measurement, when (number of moles of sulfone) / (number of moles of magnesium constituting magnesium salt) is different among the measurement peaks, based on the peak value of Raman spectrum intensity with the least change in peak position or intensity , The Raman spectrum intensity of the electrolyte and the Raman spectrum intensity of the solvent are normalized, and the Raman spectrum intensity of the solvent alone at the value RS 1 of the Raman shift of the solvent having no interaction with the electrolyte is I 11 .
  • Electrolyte solution Third aspect >> A solvent comprising sulfone, and a magnesium salt dissolved in the solvent; An electrolytic solution in which an abundance ratio of solvent molecules strongly interacting with the dissolved magnesium salt to magnesium is 0.5 or more.
  • Electrolyte solution Fourth mode >> A solvent comprising sulfone, and a magnesium salt dissolved in the solvent; The electrolytic solution whose value (Mg molar ratio) of (the number of moles of sulfone) / (the number of moles of magnesium which constitutes magnesium salt) is less than 4.
  • the sulfone is an alkyl sulfone represented by R 1 R 2 SO 2 (wherein R 1 and R 2 represent an alkyl group), or any of [A01] to [A06] consisting of an alkyl sulfone derivative
  • Alkyl sulfones are dimethyl sulfone, methyl ethyl sulfone, methyl n-propyl sulfone, methyl i-propyl sulfone, methyl n-butyl sulfone, methyl i-butyl sulfone, methyl-s-butyl sulfone, methyl -T-butylsulfone, ethylmethylsulfone, diethylsulfone, ethyl-n-propylsulfone, ethyl-i-propylsulfone, ethyl-n-butylsulfone, ethyl-i-butylsulfone, ethyl-s-butylsulfone, ethyl- t-Butyl sulfone, di-n-propyl sulfone, di-i-propyl
  • Magnesium salts include magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium perchlorate, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium trifluoroacetate, magnesium borohydride, tetrafluoroboric acid
  • magnesium thiocyanate magnesium bis (2,4,4-trimethylpentyl) phosphinate, and Hexaalkyl dicyanamide azide magnesium [Mg (HRDS) 2], where, R represents at least one magnesium salt selected from the group consisting of at
  • sulfone includes ethyl-n-propyl sulfone
  • Method of producing electrolyte solution >> A method for producing an electrolytic solution comprising a solvent comprising sulfone, and a magnesium salt dissolved in the solvent, A method for producing an electrolytic solution, wherein a magnesium salt is pulverized, mixed with a solvent, heated and stirred.
  • Sulfone is an alkyl sulfone represented by R 1 R 2 SO 2 (wherein R 1 and R 2 represent an alkyl group), or an electrolyte of an alkyl sulfone derivative [B01] or [B02] Method of producing liquid.
  • alkyl sulfone is dimethyl sulfone, methyl ethyl sulfone, methyl n-propyl sulfone, methyl i-propyl sulfone, methyl n-butyl sulfone, methyl i-butyl sulfone, methyl-s-butyl sulfone, methyl -T-butylsulfone, ethylmethylsulfone, diethylsulfone, ethyl-n-propylsulfone, ethyl-i-propylsulfone, ethyl-n-butylsulfone, ethyl-i-butylsulfone, ethyl-s-butylsulfone, ethyl- t-Butyl sulfone, di-n-propyl sulfone, di-i-propyl s
  • Magnesium salts are magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium perchlorate, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium trifluoroacetate, magnesium borohydride, tetrafluoroboric acid
  • sulfone includes ethyl-n-propyl sulfone
  • a magnesium salt is a manufacturing method of the electrolyte solution as described in [B01] or [B02] which contains magnesium chloride.
  • Magnesium Secondary Battery First Mode
  • a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and a magnesium secondary battery provided with an electrolytic solution The electrolyte comprises a solvent comprising sulfone, and a magnesium salt dissolved in the solvent, and The value of (the number of moles of sulfone) / (the number of moles of magnesium constituting the magnesium salt) (molar ratio of Mg) is 4 or less, so that the solvent in a state where the interaction with the electrolyte is weak is reduced.
  • Magnesium secondary battery consisting of electrolyte solution.
  • a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and a magnesium secondary battery provided with an electrolytic solution The electrolyte comprises a solvent comprising sulfone, and a magnesium salt dissolved in the solvent, and In Raman spectroscopy measurement, when (number of moles of sulfone) / (number of moles of magnesium constituting magnesium salt) is different among the measurement peaks, based on the peak value of Raman spectrum intensity with the least change in peak position or intensity , The Raman spectrum intensity of the electrolyte and the Raman spectrum intensity of the solvent are normalized, and the Raman spectrum intensity of the solvent alone at the value RS 1 of the Raman shift of the solvent having no interaction with the electrolyte is I 11 .
  • the Raman spectral intensity of the electrolytic solution is I 22, I 12 / I 11 ⁇ 0.6 Or 0.4 ⁇ I 22 / I 21
  • a magnesium secondary battery consisting of an electrolyte that satisfies the requirements.
  • a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and a magnesium secondary battery provided with an electrolytic solution The electrolyte comprises a solvent comprising sulfone, and a magnesium salt dissolved in the solvent, and The magnesium secondary battery which consists of electrolyte solution whose existence ratio with respect to magnesium of the solvent molecule which is strongly interacting with the melt
  • dissolved magnesium salt is 0.5 or more.
  • a magnesium secondary battery comprising a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and an electrolytic solution,
  • the electrolyte comprises a solvent comprising sulfone, and a magnesium salt dissolved in the solvent
  • a magnesium secondary battery comprising an electrolyte solution in which the ratio of the solvent having no interaction with the electrolyte to the total solvent is 3/4 or less.
  • a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and a magnesium secondary battery provided with an electrolytic solution The electrolyte comprises a solvent comprising sulfone, and a magnesium salt dissolved in the solvent, and The magnesium secondary battery which consists of electrolyte solution whose value (Mg molar ratio) of the number-of-moles of a sulfone / (the number of moles of magnesium which comprises magnesium salt) is less than four.
  • a magnesium secondary battery comprising a positive electrode member containing sulfur or a sulfur compound, a negative electrode member containing magnesium or a magnesium compound, and an electrolytic solution, The magnesium secondary battery which electrolyte solution becomes from the electrolyte solution any one of [A01] thru
  • Sulfone is an alkyl sulfone represented by R 1 R 2 SO 2 (wherein R 1 and R 2 represent an alkyl group), or any of [C01] to [C07] consisting of an alkyl sulfone derivative
  • the magnesium secondary battery as described in 1 or 2.
  • Alkyl sulfone is dimethyl sulfone, methyl ethyl sulfone, methyl-n-propyl sulfone, methyl-i-propyl sulfone, methyl-n-butyl sulfone, methyl-i-butyl sulfone, methyl-s-butyl sulfone, methyl -T-butylsulfone, ethylmethylsulfone, diethylsulfone, ethyl-n-propylsulfone, ethyl-i-propylsulfone, ethyl-n-butylsulfone, ethyl-i-butylsulfone, ethyl-s-butylsulfone, ethyl- t-Butyl sulfone, di-n-propyl sulfone, di-i-propyl s
  • Magnesium salts include magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium perchlorate, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium trifluoroacetate, magnesium borohydride, tetrafluoroboric acid
  • magnesium thiocyanate magnesium bis (2,4,4-trimethylpentyl) phosphinate, and Hexaalkyl dicyanamide azide magnesium [Mg (HRDS) 2], where, R represents at least one magnesium salt selected from the group consisting of at
  • [C11] sulfone includes ethyl-n-propyl sulfone, The magnesium salt contains magnesium chloride, The magnesium secondary battery of any one of [C01] thru
  • Battery pack A battery pack comprising a secondary battery, control means for controlling the secondary battery, and an outer package containing the secondary battery, The secondary battery is a battery pack comprising the magnesium secondary battery according to any one of [C01] to [C11].
  • [D03] ⁇ Electric vehicle> An electric vehicle having a conversion device that receives supply of power from a secondary battery and converts it into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information on the secondary battery,
  • the secondary battery is an electric vehicle comprising the magnesium secondary battery according to any one of [C01] to [C11].
  • ⁇ Power system> A power system configured to receive supply of power from a secondary battery and / or supply power from a power source to the secondary battery,
  • a secondary battery is the electric power system which consists of a magnesium secondary battery any one of [C01] thru
  • a power storage power supply comprising a secondary battery and configured to be connected to an electronic device to which power is supplied,
  • the secondary battery is a power storage power source comprising the magnesium secondary battery according to any one of [C01] to [C11].

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Abstract

La présente invention porte sur un solvant comprenant du sulfone et sur une solution électrolytique comprenant du sel de magnésium dissous dans le solvant. Dans cette solution électrolytique, une valeur (un rapport molaire Mg) obtenue en divisant le nombre de moles de sulfone par le nombre de moles de magnésium constituant le sel de magnésium est égale ou inférieure à quatre et, plus préférentiellement, inférieure à quatre et, par conséquent, le solvant dans un état de faible interaction avec un électrolyte est réduit.
PCT/JP2018/025887 2017-07-12 2018-07-09 Batterie rechargeable au magnésium, solution électrolytique et procédé de fabrication d'une solution électrolytique WO2019013165A1 (fr)

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WO2020235615A1 (fr) * 2019-05-23 2020-11-26 富士フイルム和光純薬株式会社 Batterie au magnésium
CN113690484A (zh) * 2021-08-26 2021-11-23 广东省国研科技研究中心有限公司 一种可充镁-硫电池电解液及其制备方法
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Publication number Priority date Publication date Assignee Title
WO2020235615A1 (fr) * 2019-05-23 2020-11-26 富士フイルム和光純薬株式会社 Batterie au magnésium
CN113690484A (zh) * 2021-08-26 2021-11-23 广东省国研科技研究中心有限公司 一种可充镁-硫电池电解液及其制备方法
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CN115347230A (zh) * 2022-09-14 2022-11-15 哈尔滨工业大学 一种原位生成镁盐的镁二次电池非亲核电解液及其制备方法与应用

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